Preparation and properties of high‐performance polysilsesquioxanes/bismaleimide‐triazine hybrids

A novel kind of high‐performance hybrids (coded as POSS‐NH₂/BT) with significantly decreased curing temperature, lowered dielectric constant and loss, and improved thermal resistance were developed, which were prepared by copolymerizing bismaleimide with cage octa(aminopropylsilsesquioxane) (POSS‐NH₂) to produce POSS‐containing maleimide, and then co‐reacted with 2,2′‐bis(4‐cyanatophenyl) isopropylidene. The curing behavior and typical properties of cured POSS‐NH₂/BT were systematically investigated. Results show that POSS‐NH₂/BT hybrids have lower curing temperatures than BT resin because of the additional reactions between  OCN and amine groups. Compared with BT resin, all hybrids show improved dielectric properties. Specifically, hybrids have slightly decreased dielectric constants and similar dependence of dielectric constant on frequency over the whole frequency from 10 to 10⁶ Hz; more interestingly, the dielectric loss of hybrids is only 25% of that of BT resin at the frequency lower than 10⁵ Hz, whereas all hybrids and BT resin have almost equal dielectric loss when the frequency is higher than 10⁵ Hz. In addition, POSS‐NH₂/BT hybrids also show good thermal and thermo‐oxidative stability compared with BT resin. All these differences in macroproperties are attributed to the difference in chemical structure between POSS‐NH₂/BT hybrids and BT resin. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The tribological properties of benzoxazine‐bismaleimides composites with functionalized nano‐SiO2

To improve the tribological properties of benzoxazine (BOZ) resin, bismaleimides (BMI) resin is chosen as organic phase, hyperbranched polysilane functionalized SiO₂ nanoparticles (HBPSi‐SiO₂) are chosen as inorganic modifiers to prepare HBPSi‐SiO₂/BOZ‐BMI composites using high shear and ultrasonic processes. The effect of content of HBPSi‐SiO₂ on the mechanical properties and tribological properties of the composites are investigated. The results show that suitable addition of HBPSi‐SiO₂ can largely enhance the impact strength, reduce the friction coefficient, and wear rate of BOZ‐BMI resin. Scanning electron microscopy is employed to research the wearing mechanism of materials. The severe wear of the BOZ pure resin is owing to fatigue wear, and the moderate wear of BOZ‐BMI resin is attributed to adhesive wear. While, the mild wear of the composites with HBPSi‐SiO₂ is due to abrasive wear. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

Tribological properties of bismaleimide composites with surface‐modified SiO2 nanoparticles

In this article, the surface of SiO₂ nanoparticles was modified by silane coupling agent N‐(2‐aminoethyl)‐γ‐aminopropylmethyl dimethoxy silane. The bismaleimide nanocomposites with surface‐modified SiO₂ nanoparticles or unmodified SiO₂ nanoparticles were prepared by the same casting method. The tribological performance of the nanocomposites was studied on an M‐200 friction and wear tester. The results indicated that the addition of SiO₂ nanoparticles could decrease the frictional coefficient and the wear rate of the composites. The nanocomposites with surface‐modified SiO₂ nanoparticles showed better wear resistance and lower frictional coefficient than that with the unmodified nanoparticles SiO₂. The specific wear rate and the steady frictional coefficient of the composite with 1.0 wt % surface‐modified SiO₂ nanoparticles are only 1.8 × 10^?6 mm³/N m and 0.21, respectively. The dispersion of surface‐modified SiO₂ nanoparticles in resin matrix was observed with transmission electron microscope, and the worn surfaces of pure resin matrix and the nanocomposites were observed with scanning electron microscope. The different tribological behavior of the resin matrix and the filled composites should be dependent on their different mechanical properties and wear mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation on curing reaction of phthalonitrile resin with nanosilica and the properties of their glass fiber-reinforced composites

In this work, Phthalonitrile containing benzoxazine (BA-ph) and Bisphenol A based cyanate ester (CE) were chosen as the matrix resin. Various amount of nano-SiO₂ was incorporated into BA-ph/CE and their glass fiber-reinforced composite laminates were fabricated. Curing reaction and processability of BA-ph/CE/SiO₂ blends were studied by differential scanning calorimetry and dynamic rheological analysis. Results showed that BA-ph and CE exhibited good processability and curing reaction of BA-ph/CE was not obviously affected by SiO₂. Scanning electron microscope images of the composites showed that SiO₂ particles were well dispersed in BA-ph/CE matrix. Moreover, SiO₂ could act as physical crosslinking points and diluent in matrix as well as between the glass fibers to improve the mechanical properties of composite laminates. As the results of dynamic mechanical analysis and thermogravimetry analysis, composite laminates possessed satisfactory T_g and good thermal stability. With incorporation SiO₂ particles into matrix resin, dielectric constant and dielectric loss of BA-ph/CE/SiO₂/GF composites were increased and showed frequency dependence.     

Novel high‐performance wave‐transparent aluminum phosphate/cyanate ester composites

Advanced wave‐transparent composites are the key materials for many cutting‐edge industries including aviation and aerospace, which should have outstanding heat resistance, low dielectric constant and loss as well as good mechanical properties. A novel kind of high‐performance wave‐transparent composites based on surface‐modified aluminum phosphate AlPO₄(KH‐550) and cyanate ester (CE) was first developed. The dielectric and dynamic mechanical properties of AlPO₄(KH‐550)/CE composites were investigated intensively. Results show that AlPO₄(KH‐550)/CE composites have decreased dielectric loss and higher storage moduli than pure CE resin; in addition, the composites with suitable AlPO₄(KH‐550) concentration remain the outstanding thermal property and low dielectric constant of pure CE resin. The reasons attributing to these results are discussed from the effects of AlPO₄(KH‐550) on the key aspects such as morphology, curing mechanism, and interfacial adhesion of composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of methacryl polyhedral oligomeric silsesquioxane on the thermal and mechanical properties of methylsilicone resin

A methacryl polyhedral oligomeric silsesquioxane (POSS)‐reinforced methylsilicone resin was prepared in this work. The structures of the obtained products were confirmed with Fourier transform infrared and atomic force microscopy. The influence of methacryl‐POSS on the thermal behavior of the methylsilicone resin was studied by thermogravimetric analysis and isothermal thermogravimetric analysis. The results showed that the thermal stability of the methylsilicone resin was improved, and the degree of thermooxidative degradation was lowered; this was due to the retardation of polymer chain motion and the formation of a protective layer of SiO₂. The interlaminar shear strength and flexural strength of quartz fiber/methylsilicone resin composites were tested to determine the effects of methacryl‐POSS on the mechanical properties of methylsilicone resin. The results revealed that the mechanical properties of the methylsilicone composites also increased obviously after the incorporation of methacryl‐POSS because of the increase in the cure degree and rigidity of the resin. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Tribological properties of polyimide fabric‐epoxy composites modified by hollow silica microspheres

The polyimide (PI) fabric/epoxy (EP) composites modified with different content of micro‐SiO₂ hollow spheres were prepared by dip‐coating and subsequently hot‐press process. For comparison, the pure EP and the unmodified PI fabric/EP composite were also fabricated. The differential scanning calorimetry was conducted to investigate the crosslinking reaction of composites. The results indicated that there exhibited a remarkable improvement in the mechanical and tribological properties of PI fabric/EP composites after incorporating the micro‐SiO₂. The best tribological properties were obtained when the content of micro‐SiO₂ was 2 wt%, whose wear rate was 71.9% lower than that of unmodified PI fabric/EP composite. The worn surfaces were observed by a scanning electron microscope to illustrate the friction mechanisms. Note that the skeleton network structure of fabric throughout the whole composites supported the matrix. At the same time, the microparticulates filled in the interstices of fabrics interwoven structure and the gaps between layers of fabrics, which propped up the skeleton network of fabric under the high frictional load and afford excellent interface between fabrics and EP. This ensures the outstanding tribological properties of PI fabric/EP composites. POLYM. COMPOS., 38:2283–2293, 2017. © 2015 Society of Plastics Engineers     

New composites with high thermal conductivity and low dielectric constant for microelectronic packaging

Three composites based on cyanate (CE) resin, aluminum nitride (AlN), surface‐treated aluminum nitride [AlN(KH560)], and silicon dioxide (SiO₂) for microelectronic packaging, coded as AlN/CE, AlN(KH560)‐SiO₂(KH560)/CE, and AlN‐SiO₂/CE composite, respectively, were developed for the first time. The thermal conductivity and dielectric constant of all composites were investigated in detail. Results show that properties of fillers in composites have great influence on the thermal conductivity and dielectric constant of composites. Surface treatment of fillers is beneficial to increase the thermal conductivity or reduce dielectric constant of the composites. Comparing with binary composite, when the filler content is high, ternary composites possess lower thermal conductivity and dielectric constant. The reasons leading to these outcomes are discussed intensively. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

A novel hybrid functional nanoparticle and its effects on the dielectric,mechanical, and thermal properties of cyanate ester

A novel hybrid functional nanoparticle (denoted POSS‐MPS) was synthesized by aminopropyl‐functionalized mesoporous silica (AP‐MPS) with glycidyl polyhedral oligomeric silsesquioxane (G‐POSS). The G‐POSS was employed as molecular caps to envelop the MPS and improve the interaction with the polymer matrix. The POSS‐MPS hybrids were designed to improve the properties of cyanate ester (CE) without affecting its inherent properties. The POSS‐MPS/CE composites exhibited excellent improvement in dielectric properties, mechanical properties, and thermal properties due to increase of voids volume in the composites and reinforcement of interface interaction between organic and inorganic phase. The dielectric constant (κ) and loss factor (tan δ) of composites with 4 phr of POSS‐MPS reduced to 2.78 and 0.008 in comparison to pure CE with the value of 3.27 and 0.012, respectively. Moreover, the composites exhibited 14.3, 4.9, 57.5, and 8.7% enhancement in flexural strength, flexural modulus, impact strength, and glass transition temperature (T_g) in comparison to pure CE, respectively. The results manifested that introduction of POSS‐MPS into CE exhibited toughening and reinforcing effects on the composites. POLYM. COMPOS., 37:2142–2151, 2016. © 2015 Society of Plastics Engineers     

Epoxy/POSS organic–inorganic hybrids: Viscoelastic,mechanical properties and micromorphologies

A series of epoxy resin (EP)/octa(aminpropyl)silsesquioxane (POSS‐NH₂) organic–inorganic hybrid composites (EP/POSS‐NH₂ 100/0, 95/5, 90/10, and 80/20 wt/wt) were prepared by melt casting and then curing. Viscoelastic and mechanical properties of these composites were studied by dynamic mechanical analysis and mechanical testing, respectively. Scanning electron microscopy was used to study of the micromorphologies of the composites and to elucidate the toughening mechanisms of POSS‐NH₂. POSS units incorporated into the epoxy network showed good compatibility with the resin matrix. Phase separation was not observed even at high POSS content (20 wt%). Incorporation of POSS macromer into the epoxy network after curing increased the glass transition temperature, slightly narrowed the temperature range widths of the glass transition, and lowered the intensities of their loss moduli peaks of the resultant composites. The glass transition temperature of EP/POSS‐NH₂ composites increased significantly with increasing POSS content at lower POSS content (<10 wt%), while increased slightly at higher POSS content. Both impact and flexural strengths of the hybrids reached their optimum values when 10 wt% content of POSS was introduced. POLYM. COMPOS., 28:175–179, 2007. © 2007 Society of Plastics Engineers.     

Investigation on thermal stability and tribological properties of ZrB2 particles filling cyanate ester resin composites by experiments and numerical simulation

The thermal stability and tribological properties of cyanate ester (CE) composites filled with Zirconium boride (ZrB₂) particles were investigated by experimental and numerical simulation. The results of thermogravimetric analysis and differential scanning calorimetry showed that the thermal stability of composites was improved by introduction of ZrB₂ particles. The tribological properties of composites including friction coefficient and wear rate measured by pin‐on‐disk friction and wear tester were enhanced. Friction coefficient and wear rate of composites were decreased significantly with an increase of ZrB₂ particles content under dry and oil sliding conditions. The 5 wt% ZrB₂ particles reinforced CE resin composite presented optimal thermal stability and tribological performance due to good dispersion of ZrB₂ particles. The worn surfaces of composites were observed by scanning electron microscopy to explore wear mechanism, indicating that the dominant wear mechanism of composites was transformed from adhesive wear to abrasive wear after incorporation of ZrB₂ particles. Finite element model was established to study the distribution of friction stress. The results revealed that filling ZrB₂ particles in the friction process of composites could bear more friction stress than CE resin matrix, which further illustrated that abrasive wear is main wear mechanism of ZrB₂/CE resin composites. POLYM. ENG. SCI., 59:602–607, 2019. © 2018 Society of Plastics Engineers     

环氧树脂/石英纤维透波复合材料制备

为改善环氧树脂的介电性能及提升石英纤维的界面性能,使用缩水甘油醚基笼型倍半硅氧烷(G-POSS)和γ-氨丙基三乙氧基硅烷(KH-550)分别对环氧树脂和石英纤维进行改性.利用差示扫描量热法研究改性后环氧树脂的固化过程,并通过外推法确定了其固化工艺,根据固化工艺制备环氧树脂/石英纤维复合材料,分别对该复合材料的热稳定性、...     

Effect of SiO2 nanoparticles-decorated SCF on mechanical and tribological properties of cenosphere/SCF/PEEK composites

A silicon oxide (SiO₂) nanoparticles-decorated short carbon fiber (SCF) hybrid (SCF-SiO₂) was designed to improve the weak interfacial bonding between fibers and matrix. Nano-SiO₂ was grafted onto carbon fibers by introducing amino group and epoxy group on the surface of carbon fibers and SiO₂, respectively. The chemical composition of SCF-SiO₂ was analyzed by Fourier transform infrared spectrometer and energy-dispersive spectrometry, the microstructure of SCF-SiO₂ were investigated by scanning electron microscope, and then the hybrid filler was introduced into Poly(ether ether ketone) (PEEK). Due to the strong interfacial interaction between filler and matrix, the mechanical and tribological properties of SCF-SiO₂/PEEK composites were significantly better than SCF/PEEK composites. In order to further improve the tribological properties of the composites, micrometer-sized cenosphere (CS) particles were introduced into the aforementioned system to prepare multicomponent composites. The test results of friction and wear indicate that the CS/SCF-SiO₂/PEEK composites have the optimal tribological properties. Compared with pure PEEK, the friction coefficient of CS/SCF-SiO₂/PEEK composites under 200 N load decreases by 56.4% and the specific wear rate decreases by 87.4%. Meanwhile, the thermal decomposition temperature of CS/SCF-SiO₂/PEEK composites is increased by 40 °C compared to pure PEEK. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48749.     

Enhancing the thermal conductivities of SiO2/Epoxy composites by orientation

To improve the thermal conductivity of epoxy resin, tensile way was used to orient the molecular chain of epoxy resin with SiO₂ particles filled. In this article, SiO₂/Epoxy composites which had approximately one‐dimensional lattice structure were prepared. The heat generated by LED chip rapidly passed along the direction of the one‐dimensional orientation in SiO₂/Epoxy composites. The results showed that the thermal conductivity of oriented composites increased with the increase of silica concentration and draw ratio (If S is the cross‐sectional areas of composites at the mold outlet, S₀ is the cross‐sectional areas of composites after molding set, and draw ratio is S/S₀). With the addition of 50 wt% SiO₂ to the epoxy resin, the thermal conductivity of oriented SiO₂/Epoxy composites with the draw ratio of 4 was 0.873 W/m K, which was 2.55 times that of unoriented SiO₂/Epoxy composites. And a thermal conductivity, 5.97 times that of the epoxy resin, was obtained with 80 wt% SiO₂ and the draw ratio of 4. Nevertheless, the relative permittivities of epoxy composites which had 50 wt% SiO₂ with the draw ratio of 4 are stable with increasing frequency. POLYM. COMPOS., 37:818–823, 2016. © 2014 Society of Plastics Engineers     

Effect of nanosilica on the thermal,mechanical, and dielectric properties of polyarylene ether nitriles terminated with phthalonitrile

Nanosilica/polyarylene ether nitriles terminated with phthalonitrile (SiO₂/PEN‐t‐Ph) composites were prepared by hot‐press approach. To ensure the nano‐SiO₂ can disperse uniformly, the solution casting method combined with ultrasonic dispersion technology had been taken previously. The mass fraction of nano‐SiO₂ particles was varied to investigate their effect on the thermal, mechanical, and dielectric properties of the nanocomposites. From scanning electron microscope images, it was found that the nanoSiO₂ particles were dispersed uniformly in the PEN‐t‐Ph matrix when the addition of nano‐SiO₂ was less than 16.0 wt%. However, when the mass fraction of nano‐SiO₂ increased to 20.0 wt%, the nano‐SiO₂ particles tend to self‐aggregate and form microns sized particles. Thermal studies revealed that nano‐SiO₂ particles did not weaken the thermal stabilities of the PEN‐t‐Ph matrix. Mechanical investigation manifested that the SiO₂/PEN‐t‐Ph nanocomposites with 12.0 wt% nano‐SiO₂ loading showed the best mechanical performance with tensile strength of 108.2 MPa and tensile modulus of 2107.5 Mpa, increasing by 14% and 19%, respectively as compared with the pure PEN‐t‐Ph film. Dielectric measurement showed that the dielectric constant increased from 3.70 to 4.15 when the nano‐SiO₂ particles varied from 0.0 to 20.0 wt% at 1 kHz. Therefore, such composite was a good candidate for high performance materials at elevated temperature environment. POLYM. COMPOS., 35:344–350, 2014. © 2013 Society of Plastics Engineers     

Curing reactions and properties of organic–inorganic composites from hydrogenated carboxylated nitrile rubber and epoxycyclohexyl polyhedral oligomeric silsesquioxanes

Novel organic–inorganic composites were prepared by curing hydrogenated carboxylated nitrile rubber (HXNBR) with epoxycyclohexyl polyhedral oligomeric silsesquioxanes (POSS) through chemical bonding of carboxyl groups of HXNBR and epoxy groups of POSS. The process of the curing reaction was investigated using in situ Fourier transform infrared spectroscopy. The reaction order, the activation energy and the frequency factor were obtained through a kinetic analysis using differential scanning calorimetry. Through dynamic mechanical analysis, the glass transition temperature, crosslink density and degree of heterogeneity of the composites were estimated, and they showed an increasing tendency with increasing POSS content. The results of dielectric property measurements showed that the dielectric constant of the composites decreased with increasing POSS content in the studied frequency range. Copyright © 2010 Society of Chemical Industry     

Low dielectric and high thermal conductivity epoxy nanocomposites filled with NH2‐POSS/n‐BN hybrid fillers

Hybrid fillers of mono‐amine polyhedral oligomeric silsesquioxane/nanosized boron nitride (NH₂‐POSS/n‐BN) were performed to fabricate NH₂‐POSS/n‐BN/epoxy nanocomposites. Results revealed that the dielectric constant and dielectric loss values were decreased with the increasing addition of NH₂‐POSS obviously, but increased with the increasing addition of BN fillers. For a given loading of NH₂‐POSS (5 wt %), the thermal conductivities of NH₂‐POSS/n‐BN/epoxy nanocomposites were improved with the increasing addition of n‐BN fillers, and the thermal conductivity of the nanocomposites was 1.28 W/mK with 20 wt % n‐BN fillers. Meantime, the thermal stability of the NH₂‐POSS/n‐BN/epoxy nanocomposites was also increased with the increasing addition of n‐BN fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41951.     

Influence of dielectric barrier effect and thermally-conductive network on thermal and electrical properties of epoxy under different frequencies and temperatures

Epoxy resin (EPR) insulations play a vital role in the insulation of modern power electronic equipment owing to their excellent dielectric properties. However, due to the high-power density and miniaturization of power equipment which causes high heat fluxes under high voltage and high-frequency stresses, EPR with good thermal and insulation properties is urgently needed. In this study, the polydopamine functionalized micro-BN and core-shell nano TiO₂–SiO₂ particles are dispersed in EPR to simultaneously improve thermal and dielectric insulation properties. It is revealed that the addition of micro-nano particles significantly improves the thermal and dielectric performance. Particularly, the high thermal conductivity of micro-BN and the dielectric barrier effect due to the core-shell structure of nano TiO₂–SiO₂ are the main reasons for improved thermal and dielectric insulation performance, respectively. The EPR composite containing 3 wt% of micro-BN and 1 wt% of nano TiO₂–SiO₂ exhibits the optimal performance with 0.49 W/mK thermal conductivity and the highest dielectric strength among all the samples, that is, 60.61 kV/mm even at 10 kHz and 90°C. This study found that the crucial factors are the surface encapsulation, weight percent, and homogeneous dispersion of particles in EPR, the dielectric barrier effect, thermal conductivity, and the mismatch between the dielectric constant of EPR and particles. This study proposes the optimal weight percent of suitable micro-nano particles for EPR to produce suitable composites for high-frequency and high-temperature applications.     

Synthesis,thermal properties,and flame retardance of the epoxy‐silsesquioxane hybrid resins

Epoxy/silsesquioxane‐OH (EP‐SDOH, ED) hybrid resins were prepared from cyclohexyl‐disilanol silsesquioxane (SDOH) and diglycidyl ether of bisphenol A via the reaction between silanol and the oxirane group, with the cobalt naphthanate as a catalyst. It was found that incorporation of SDOH allows the reaction between oxirane ring and Si? OH, and the silsesquioxane cage structure can be the main chain or as the side chain of the hybrid resin. The EP‐SDOH hybrid resins with various SDOH contents were cured by 4,4′‐diaminodiphenylsulphone, and the curing reaction was investigated by differential scanning calorimetry. The curing characteristics of EP‐SDOH hybrids had been observed to be influenced by the content of SDOH in the hybrid. The differential scanning calorimetry thermograms indicated that the EP‐SDOH hybrid exhibited a higher initial temperature, peak temperature, as well as final temperature than those of the pure epoxy resin when cured by the same curing agent 4,4′‐diaminodiphenylsulphone. The curing kinetic parameters were calculated by using the Ozawa method and the results indicated that EP‐SDOH hybrids possess the same curing mechanism as the pure epoxy resin. The properties of the cured EP‐SDOH hybrid resins such as the glass transition temperature (T_g), dynamic mechanical analysis, thermal stability, as well as the flame retardance were also investigated, and the results showed that introducing silsesquioxane‐OH unit into epoxy resin successfully modified the local structure, made the chain stiffness, restrict the chain mobility, and eventually improved thermal stability and flame retardance of epoxy resin. POLYM. ENG. SCI., 47:225–234, 2007. © 2007 Society of Plastics Engineers.